Toner

ABSTRACT

Toners are provided which may comprise toner particles, a colorant, and optionally, a wax, wherein the toner particles comprise a resin comprising a polymerization product of reactants comprising a dioxane/dioxolane monomer and a vinyl co-monomer, wherein the dioxane/dioxolane monomer is an ester of (meth)acrylic acid with an alcohol comprising a dioxane moiety, an ester of (meth)acrylic acid with an alcohol comprising a dioxolane moiety, or both.

CROSS-REFERENCE TO RELATED APPLICATIONS

The present application is a continuation of U.S. patent applicationSer. No. 17/386,095, filed Jul. 27, 2021, the entire contents of whichare incorporated herein by reference.

BACKGROUND

Many styrene-acrylate-based resins have been developed and used toprovide a variety of toners, generally via emulsion aggregationprocesses, encompassing a broad range of desirable properties. However,emission of volatile organic compounds (VOCs) can be an issue when usingsuch toners in multi-function printers under certain conditions, e.g.,in confined spaces with limited air circulation or running at high printspeeds over extended periods of time. To address this issue, residualmonomer levels have been kept low, processes for making the resins andtoners have been improved, and carbon filters have been added toprinters.

SUMMARY

The present disclosure provides latexes comprising resin particlespolymerized from dioxane/dioxolane monomers. The latexes may be used toform a variety of compositions, including toners and paints, which arealso encompassed by the present disclosure. At least embodiments of thedioxane/dioxolane-based resin particles provide toners exhibitingreduced VOC emission while maintaining excellent printing performance.

In one aspect, a toner is provided which comprises toner particles, acolorant, and optionally, a wax, wherein the toner particles comprise aresin comprising a polymerization product of reactants comprising adioxane/dioxolane monomer and a vinyl co-monomer, wherein thedioxane/dioxolane monomer is an ester of (meth)acrylic acid with analcohol comprising a dioxane moiety, an ester of (meth)acrylic acid withan alcohol comprising a dioxolane moiety, or both.

Other principal features and advantages of the disclosure will becomeapparent to those skilled in the art upon review of the followingdetailed description and the appended claims.

DETAILED DESCRIPTION

Latex

In one aspect, latexes are provided. Such a latex comprises resinparticles synthesized from various monomers, forming a polymericmaterial from which the resin particles are composed. At least one typeof monomer is used which is an ester of (meth)acrylic acid with analcohol comprising a dioxane moiety or an alcohol comprising a dioxolanemoiety. (The use of “(meth)” as in, e.g., “(meth)acrylic acid”, refersto both acrylic acid and methacrylic acid.) In the present disclosure,this type of monomer may be referred to as an “dioxane/dioxolanemonomer.” This phrase, dioxane/dioxolane monomer, encompasses themonomer which is the ester of (meth)acrylic acid with the alcoholcomprising the dioxane moiety, the monomer which is the ester of(meth)acrylic acid with the alcohol comprising the dioxolane moiety, andboth such monomers. The dioxane moiety may be a 1,3-dioxane moiety andthe dioxolane moiety may be a 1,3-dioxolane moiety. The alcoholcomprising the dioxane/dioxolane moiety may be an acetal of a triol, aketal of a triol, or a carbonate of a triol. Illustrative triols includeglycerol and trimethylolpropane. The triol may be unsubstituted orsubstituted. By “substituted” it is meant that one or more bonds to acarbon(s) or hydrogen(s) are replaced by a bond to non-hydrogen andnon-carbon atoms. The dioxane/dioxolane monomer may have Formula I(dioxane) or II (dioxolane) as shown below, wherein R is selected fromhydrogen and methyl; R′ is selected from hydrogen and ethyl; and Z isselected from hydrogen, an oxygen of a carbonyl group, an alkyl group,an aryl group, and an alkoxy group. Either or both types of monomers maybe used in the resin particles.

The carbonyl group refers to a C═O group, that is Z is O covalentlybound to the carbon via a double bond, thereby forming a carbonyl groupbetween the two oxygens of the 5 or 6-membered ring.

The alkyl group may be linear or branched. The alkyl group may have from1 to 20 carbons. This includes having from 1 to 18 carbons and from 1 to10 carbons, e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 carbons. The alkylgroup may be substituted or unsubstituted. The aryl group may bemonocyclic having one aromatic ring, e.g., benzene, or polycyclic havingone or more fused rings. The aryl group may be unsubstituted orsubstituted as described above with respect to the alkyl group, althoughsubstituted aryl groups also encompass aryl groups in which a bond to ahydrogen(s) is replaced by a bond to an unsubstituted or substitutedalkyl group as described above. The alkoxy group refers to an —O-alkylgroup.

Illustrative dioxane/dioxolane monomers include glycerol formal(meth)acrylate, trimethylolpropane formal (meth)acrylate, andisopropylideneglycerol (meth)acrylate. A single type or combinations ofdifferent types of dioxane/dioxolane monomers may be used. Inembodiments, however, the dioxane/dioxolane monomer is glycerol formal(meth)acrylate. In the present disclosure, the name “glycerol formal(meth)acrylate” (as well as the names of the other dioxane/dioxolanemonomers described in this paragraph) refers to either the dioxaneisomer, the dioxolane isomer, or both. That is, all possibilities areencompassed by the names.

At least one vinyl co-monomer is also used to form the resin particles.Illustrative vinyl co-monomers include the following: styrene, acrylate,methacrylate, butadiene, and isoprene. Illustrative vinyl co-monomersalso include acidic and basic such monomers such as the following:acrylic acid, methacrylic acid, acrylamide, methacrylamide, quaternaryammonium halides of dialkyl or trialkyl acrylamides or methacrylamide,vinylpyridine, vinylpyrrolidone, vinyl-N-methylpyridinium chloride.Illustrative vinyl co-monomers also include those comprising acarboxylic acid group such as the following: acrylic acid, methacrylicacid, itaconic acid, beta-carboxyethyl acrylate (β-CEA), 2-carboxyethylmethacrylate, maleic acid, and cinnamic acid. A single type orcombinations of different types of vinyl co-monomers may be used. Inembodiments, at least two vinyl co-monomers are used comprising styreneand an alkyl (meth)acrylate (e.g., methyl (meth)acrylate, ethyl(meth)acrylate), butyl (meth)acrylate), or combinations thereof. Thus,the alkyl group of the alkyl (meth)acrylates may have 1 or more carbons,2 or more carbons, 4 or more carbons, or from 1 to 6 carbons. Inembodiments, at least three vinyl co-monomers are used comprisingstyrene, an alkyl (meth)acrylate, and a vinyl co-monomer comprising acarboxylic acid group. In embodiments, the alkyl (meth)acrylate isn-butyl acrylate. In embodiments, the third vinyl co-monomer is β-CEA.

A crosslinking agent may be used to form the resin particles.Illustrative crosslinking agents include decanediol diacrylate (ADOD),trimethylolpropane, pentaerythritol, trimellitic acid, pyromelliticacid, and combinations thereof. The crosslinking agent may also bereferred to as a branching agent.

A chain transfer agent may be used to form the resin particles. Thechain transfer agent may be a mercaptan or a thiol. Suitable chaintransfer agents include n-dodecylmercaptan (NDM), n-dodecanethiol (DDT),tert-dodecylmercaptan, 1-butanethiol, 2-butanethiol, octanethiol, andcombinations thereof. Halogenated carbons such as carbon tetrabromide,carbon tetrachloride, and combinations thereof may be used as chaintransfer agents.

In embodiments, certain monomers may be excluded in forming the resinparticles. Excluded monomers may include one or more of the following:vinyl-imidazolium monomers, urethane (meth)acrylate monomers, and silylester monomers such as (meth)acrylic acid triisoproylsilyl ester.

In forming the latex comprising the resin particles, variouscombinations of the monomers described above may be used in a monomeremulsion comprising a solvent, an initiator (which may be included inthe monomer emulsion as stated here, or separately added in a distinctstep(s) during the polymerization process), and optionally, one or moreof the crosslinking agent, the chain transfer agent, and a surfactant.Water is generally used as the solvent, but water-soluble orwater-miscible organic solvents (e.g., ethanol) may also be included.

The type of monomers used in the monomer emulsion and their relativeamounts may be selected to tune the properties of the resin particles.This includes adjustment of the relative amount of the dioxane/dioxolanemonomer and the vinyl co-monomer (including two or three such vinylco-monomers) to achieve the T_(g) values described below. Similarly, thepresence, type, and amount of crosslinking agent and chain transferagent may also be selected to tune the properties of the resinparticles.

The dioxane/dioxolane monomer may be used in the monomer emulsion in anamount, e.g., in a range of from 1 weight % to 50 weight %, 5 weight %to 40 weight %, and 5 weight % to 30 weight %. (Here, weight % refers tothe (total weight of dioxane/dioxolane monomers)/(total weight ofmonomers, crosslinking agents (if present), and chain transfer agents(if present) in the monomer emulsion)*100). The vinyl co-monomer may beused in the monomer emulsion in an amount, e.g., in a range of from 50weight % to 98 weight %, from 60 weight % to 90 weight %, and from 65weight % to 85 weight %. (Here, weight % refers to the (total weight ofvinyl co-monomers)/(total weight of monomers, crosslinking agents (ifpresent), and chain transfer agents (if present) in the monomeremulsion)*100). In embodiments in which more than one type of vinylco-monomer is used, e.g., two or three, a first vinyl co-monomer (e.g.,styrene) may make up, e.g., from 40 weight % to 95 weight % of the totalweight of vinyl co-monomers; a second vinyl co-monomer (e.g., an alkyl(meth)acrylate) may make up, e.g., at least 15 weight %, at least 30weight %, from 5 weight % to 60 weight % of the total weight of vinylco-monomers; and a third vinyl co-monomer (e.g., (3-CEA) may make up,e.g., up to 10 weight % of the total weight of vinyl co-monomers. Otherranges for the first vinyl co-monomer include, e.g., from 50 weight % to80 weight % and from 50 weight % to 70 weight %; for the second vinylco-monomer include, e.g., from 10 weight % to 50 weight %, and from 10weight % to 30 weight %; and for the third vinyl co-monomer, e.g., from0.1 weight % to 8 weight % and from 0.1 weight % to 5 weight %.Regarding an alkyl (meth)acrylate as a possible vinyl co-monomer, inembodiments, it is present at an amount of at least 15 weight % of thetotal weight of monomers, crosslinking agents (if present), and chaintransfer agents (if present) in the monomer emulsion. This includes atleast 20 weight % and at least 25 weight %.

The crosslinking agent, if used, may be present in the monomer emulsionat an amount, e.g., up to 20 weight %, from 0.01 weight % to 20 weight%, from 0.1 weight % to 5 weight %. (Here, weight % refers to the (totalweight of crosslinking agents)/(total weight of monomers, crosslinkingagents, and chain transfer agents (if present) in the monomeremulsion)*100).

The chain transfer agent if used, may be present in the monomer emulsionat an amount, e.g., up to 10 weight %, from 0.05 weight % to 10 weight%, from 0.25 weight % to 5 weight %. (Here, weight % refers to the(total weight of chain transfer agents)/(total weight of monomers,crosslinking agents (if present), and chain transfer agents in themonomer emulsion)*100).

The initiator initiates the polymerization reactions between the variousmonomers in the monomer emulsion. Examples of suitable initiatorsinclude water soluble initiators, such as ammonium persulfate (APS),sodium persulfate and potassium persulfate. Other water-solubleinitiators which may be used include azoamidine compounds, for example2,2′-azobis(2-methyl-N-phenylpropionamidine) dihydrochloride,2,2′-azobis[N-(4-chlorophenyl)-2-methylpropionamidine]di-hydrochloride,2,2′-azobis[N-(4-hydroxyphenyl)-2-methylpropionamidine]dihydrochloride,2,2′-azobis[N-(4-amino-phenyl)-2-methylpropionamidine]tetrahydrochloride,2,2′-azobis[2-methyl-N-(phenylmethyl)propionamidine]dihydrochloride,2,2′-azobis[2-methyl-N-2-propenylpropionamidine]dihydrochloride,2,2′-azobis[N-(2-hydroxy-ethyl)2-methylpropionamidine]dihydrochloride,2,2′-azobis[2(5-methyl-2-imidazolin-2-yl)propane]dihydrochloride,2,2′-azobis[2-(2-imidazolin-2-yl)propane]dihydrochloride,2,2′-azobis[2-(4,5,6,7-tetrahydro-1H-1,3-diazepin-2-yl)propane]dihydrochloride,2,2′-azobis[2-(3,4,5,6-tetrahydropyrimidin-2-yl)propane]dihydrochlo-ride,2,2′-azobis[2-(5-hydroxy-3,4,5,6-tetrahydropyrimidin-2-yl)propane]di-hydrochloride,2,2′-azobis{2-[1-(2-hydroxyethyl)-2-imidazolin-2-yl]propane}dihydrochloride, and combinations thereof. Redox initiators may be used.As noted above, the initiator may be added separately, in distinctstep(s) in the polymerization process. The initiator may be added as aninitiator solution comprising the initiator and a solvent, e.g., water.Amounts of initiator used include those, e.g., in a range of from 0.1weight % to 5 weight %. (Here, weight % refers to the (total weight ofinitiators)/(total weight of monomers in the monomer emulsion)*100.)

A surfactant may be used in the monomer emulsion which may be selectedfrom anionic surfactants, cationic surfactants, nonionic surfactants,and combinations thereof. Amounts may be, e.g., up to 5 weight %, from0.01 weight % to 5 weight %. ((Here, weight % refers to the (totalweight of surfactants)/(total weight of monomers in the monomeremulsion)*100). Examples of anionic surfactants include sulfates andsulfonates, disulfonates, such as sodium dodecylsulfate (SDS), sodiumdodecylbenzene sulfonate, sodium dodecylnaphthalene sulfate and thelike; dialkyl benzenealkyl sulfates; acids, such as palmitic acid, andNEOGEN or NEOGEN SC available from Daiichi Kogyo Seiyaku, and the like.Other suitable anionic surfactants include DOWFAX™ 2A1, analkyldiphenyloxide disulfonate, available from The Dow Chemical Companyand TAYCA POWER BN2060, a branched sodium dodecyl benzene sulfonate,available from Tayca Corporation (Japan).

Examples of cationic surfactants include alkylbenzyl dimethyl ammoniumchloride, dialkyl benzenealkyl ammonium chloride, lauryl trimethylammonium chloride, alkylbenzyl methyl ammonium chloride, alkyl benzyldimethyl ammonium bromide, benzalkonium chloride, cetyl pyridiniumbromide, trimethyl ammonium bromide, halide salts of quarternizedpolyoxyethylalkylamines, dodecylbenzyl triethyl ammonium chlorides,M1RAPOL® and ALKAQUAT® available from Alkaril Chemical Company, SANISOL®(benzalkonium chloride) available from Kao Chemicals, and the like.

Examples of nonionic surfactants include polyoxyethylene cetyl ether,polyoxyethylene lauryl ether, polyoxyethylene octyl ether,polyoxyethylene octylphenyl ether, polyoxyethylene oleyl ether,polyoxyethylene sorbitan monolaurate, polyoxyethylene stearyl ether,polyoxyethylene nonylphenyl ether, dialkylphenoxy poly(ethyleneoxy)ethanol, and the like. Commercially available surfactants fromRhone-Poulenc such as IGEPAL CA-210™, IGEPAL CA520™, IGEPAL cA-720™,IGEPAL cO890™, ANTAROX 890™, IGEPAL CO-720™, IGEPAL CO-290™, IGEPALCA-210™ and ANTAROX 897™ may be selected. Other examples of suitablenonionic surfactants include a block copolymer of polyethylene oxide andpolypropylene oxide, including those commercially available asSYNPERONIC® PR/F and SYNPERONIC® PR/F 108.

The latex comprising the resin particles may be prepared using seededemulsion polymerization. Such a technique may involve preparing asurfactant solution in a suitable reactor. In a separate vessel, amonomer emulsion may be prepared having any of the compositionsdescribed above, e.g., comprising a dioxane/dioxolane monomer, two orthree vinyl co-monomers, a chain transfer agent, and a surfactant. Analiquot of the monomer emulsion (e.g., from 0.5% to 10% of the totalamount of the monomer emulsion) may be added to the surfactant solutionin the reactor. An initiator solution may be added to the reactor inorder to allow seed particle formation. An additional amount of themonomer emulsion (e.g., the remaining amount) may be fed into thereactor to grow the seeds to a desired size. Reaction conditions, e.g.,mixing, heating, etc., used during the steps are selected to facilitatepolymerization and to provide resin particles having desired properties.Illustrative reaction conditions are described in the Examples below.Reaction conditions described in U.S. Pat. Nos. 6,841,329 and 7,413,842,each of which is hereby incorporated by reference in its entirety, mayalso be used.

The seeded emulsion polymerization technique described above providesthe latex comprising the resin particles dispersed in the solvent. Thelatex may be used as is to form any of the toners described herein.However, further processing steps may be used, e.g., to recover theresin particles from the solvent. These processing steps include, e.g.,filtration, drying, centrifugation, spray drying, freeze drying, etc.

The resin particles formed by the seeded emulsion polymerizationtechnique described above may be characterized by their composition. Asnoted above, the polymeric material of the resin particles is the resultof polymerization reactions between various combinations of monomers toform a polymerization product. For clarity, the composition of thepolymeric material/resin particles may be identified by reference to themonomers which are polymerized, recognizing that the chemical form ofthose monomers is generally altered as a result of the polymerizationreactions. The polymerization product, and thus, the resin particles,may comprise other components present in the emulsion described above.For example, initiators (or a portion thereof, e.g., a sulphate group)may become incorporated at the beginning and end of polymer chains.Similarly, crosslinking agents, if used, are generally incorporated intopolymer chains. Surfactants, if used, may become entangled with polymerchains and become embedded within the resin particles, e.g., due tostrong noncovalent binding or adsorption forces.

In embodiments, the resin particles comprise (or consist of) apolymerization product of reactants comprising a dioxane/dioxolanemonomer, a vinyl co-monomer, an initiator, and optionally, acrosslinking agent. Any of the dioxane/dioxolane monomers, vinylco-monomers, crosslinking agents, and initiators described herein may beused. In embodiments, the resin particles comprise (or consist of) apolymerization product of reactants comprising a dioxane/dioxolanemonomer, two different vinyl co-monomers, an initiator, and optionally,a crosslinking agent. In embodiments, the resin particles comprise (orconsist of) a polymerization product of reactants comprising adioxane/dioxolane monomer, three different vinyl co-monomers, aninitiator, and optionally, a crosslinking agent. In each of theseembodiments, the monomers, crosslinking agent, initiator may be presentin the resin particles in the amounts described above. (Experiments haveshown that the conversion of the monomers is above 99.9%.) For example,the amount of the dioxane/dioxolane monomers may be in a range of from 1weight % to 50 weight % in the resin particles. As above, this weight %refers to the (total weight of dioxane/dioxolane monomers)/(total weightof monomers, crosslinking agents (if present), and chain transfer agents(if present) in the resin particles)*100.

In any of the embodiments referenced in the paragraph above, one or moreof the following variations may be used. Glycerol formal methacrylatemay be used as the dioxane/dioxolane monomer. Styrene, an alkyl(meth)acrylate (e.g., n-butyl acrylate), a vinyl co-monomer comprising acarboxylic acid group (e.g., β-CEA), and combinations thereof may beused as the vinyl co-monomer. Decanediol diacrylate may be used as thecrosslinking agent.

Using a specific, illustrative composition, the composition of the resinparticles may also be identified as poly[(styrene)-ran-(n-butylacrylate)-ran-(glycerol formal (meth)acrylate)-ran-(β-CEA)], including acrosslinked version thereof. In this description, the different chemicalmoieties which result from the polymerization reactions is identified byreference to the corresponding monomer in its parenthesis and “ran”refers to the random incorporation of the different monomers into thecopolymer. The use of this description encompasses the presence of aninitiator (or portion thereof) at the beginning of each copolymer chain,as well as crosslinking via the crosslinking agents (if present).

In embodiments in which certain monomers are excluded from forming theresin particles, it follows that such monomers do not participate in thepolymerization reactions to form the polymeric matrix of the resinparticles. Thus, in these embodiments, the composition of the resinparticles may be described as being free of (i.e., not comprising) oneor more of vinyl-imidazolium monomers, urethane (meth)acrylate monomers,and silyl ester monomers such as (meth)acrylic acid triisoproylsilylester.

In embodiments, the latex may be described as being free of (i.e., notcomprising) a resin/polymer other than what is provided by the resin ofthe present resin particles themselves. This includes being free of apolyurethane, a polyurethane (meth)acrylate, a poly(meth)acrylate (otherthan the resin particles themselves), a polyester, a silyl estercopolymer, a silyl (meth)acrylate polymer, or combinations thereof.

Since the resin/polymer making up the resin particles has already beenpolymerized, the latex itself is generally not curable and as such, isfree of (i.e., does not comprise) an initiator. This does not precludethe presence of a minor amount of unreacted initiator or reactedinitiator which may be incorporated into polymer chains. Similarly, thelatex may be described as being free of (i.e., not comprising monomers).

In embodiments, the latex may also be described as being free of (i.e.,not comprising) a fungicide/biocide such as medetomidine.

The water content of the latexes may be at least 50 weight %. Thisincludes at least 60 weight % and at least 70 weight %. These weight %refer to the weight of water as compared to the total weight of thelatex.

The resin particles may be characterized by their size. The size of theresin particles may be reported as a D₅₀ particle size, which refers toa diameter at which 50% of the sample (on a volume basis) is comprisedof particles having a diameter less than said diameter value. Inembodiments, the resin particles have a D₅₀ particle size in a range offrom 100 nm to 400 nm. This includes, e.g., a range of from 100 nm to300 nm, and from 200 nm to 350 nm. The D₅₀ particle size may bereferenced to a value measured at a pH in a range of from 2 to 3. TheD₅₀ particle size may be measured using a Nanotrac 252 instrument. Thisinstrument uses a laser light-scattering technique, in whichDoppler-shifted light generated from each particle in motion (Brownianmotion) is measured. The signals generated by these shifts areproportional to the size of the particles. The signals aremathematically converted to particle size and size distribution. Theanalysis can be performed using an external probe or by inserting theprobe into a fixed sample chamber. For light scattering techniques, NISTpolystyrene Nanosphere control samples with a diameter within the rangeof 15 mm to 300 mm under the tradename NIST Traceable Reference Materialfor Nanotrac Particle Size Analyzers obtained from Microtrac may be usedto calibrate the instrument.

The resin particles may be characterized by their onset glass transitiontemperature (T_(g)). The T_(g) values may be measured as described inthe Examples, below. In embodiments, the T_(g) is in a range of from 40°C. to 90° C. This includes a range of from 45° C. to 85° C., and from50° C. to 75° C.

The polymeric material (resin) of the resin particles may becharacterized by its weight average molecular weight (M_(w)) and itsnumber average molecular weight (M_(n)), measured as described in theExamples, below. The M_(w) may be in a range of from 25,000 Daltons to75,000 Daltons. This includes, e.g., from 30,000 Daltons to 70,000Daltons and from 40,000 Daltons to 60,000 Daltons. The M_(n) may be in arange of from 10,000 Daltons to 30,000 Daltons. This includes, e.g.,from 15,000 Daltons to 25,000 Daltons and from 20,000 Daltons to 30,000Daltons.

Toner

Any of the latexes described above may be utilized to form a tonercomprising toner particles. The composition of the toner particlesdepends upon the composition of the resin particles of the latex(es)used. However, the toner may include other components, such as a wax, acolorant, and other additives. In making the toner, such waxes,colorants, and other additives may be utilized in dispersions comprisingany of the solvents and surfactants described above.

Wax

A wax may be combined with the latex described above in forming thetoner particles. A single type or a combination of different types ofwax may be used. The wax may be present in various suitable amounts, forexample, in a total amount of from about 3% to about 20% by weight ofthe toner particles, including from about 4% to about 20% by weight ofthe toner particles, and from about 5% to about 15% by weight of thetoner particles.

Illustrative waxes include the following: an alkylene wax (such as analkylene wax having from 1 to 25 carbon atoms), a polyethylene wax, apolypropylene wax, a paraffin wax, and a Fischer Tropsch wax (such asFNP-0092® available from Nippon Seiro comprising a Fischer-Tropsch waxcontaining 42 carbon atoms). Polypropylenes and polyethylenescommercially available from Allied Chemical and Petrolite Corporationmay be used. Wax emulsions available from Michaelman Inc. and theDaniels Products Company may be used. Epolene N15™ commerciallyavailable from Eastman Chemical Products, Inc.; Viscol 550P™, a lowweight average molecular weight polypropylene available from Sanyo KaseiK. K.; and similar waxes may be used. The commercially availablepolyethylenes are believed to possess a molecular weight of about 1,000to about 5,000, and the commercially available polypropylenes arebelieved to possess a molecular weight of about 4,000 to about 10,000.Examples of functionalized waxes which may be used include amines,amides, for example Aqua Superslip 6550™, Superslip 6530™ available fromMicro Powder Inc., fluorinated waxes, for example Polyfluo 190™,Polyfluo 200™, Polyfluo S23XF™, Aqua Polyfluo 411™, Aqua Polysilk 19™,Polysilk 14™ available from Micro Powder Inc., mixed fluorinated, amidewaxes, for example Microspersion 19™ also available from Micro PowderInc., imides, esters, quaternary amines, carboxylic acids or acrylicpolymer emulsion, for example Joncryl 74™, 89™, 130™, 537™, and 538™,all available from SC Johnson Wax, chlorinated polypropylenes andpolyethylenes available from Allied Chemical and Petrolite Corporationand SC Johnson Wax. A single type or a combination of different types ofwax may be used.

Colorants

A colorant may be combined with the latex described above in forming thetoner particles. A single type or a combination of different types ofcolorants may be used. Colorants include, for example, pigments, dyes,mixtures thereof, such as mixtures of dyes, mixtures of pigments,mixtures of dyes and pigments, and the like. The colorant may be addedin amounts sufficient to impart the desired, color, hue, and shade. Thecolorant may be present in a total amount of, for example, from about 1%to about 25% by weight of the toner particles, including from about 1%to about 20% by weight of the toner particles, or from about 2% to about15% by weight of the toner particles.

Carbon black, which is available in forms, such as furnace black,thermal black, and the like is a suitable colorant. Carbon black may beused with one or more other colorants, such as a cyan colorant, toproduce a desired hue.

Examples of cyan pigments include copper tetra(octadecylsulfonamido)phthalocyanine, a copper phthalocyanine colorant listed in the ColorIndex (CI) as CI 74160, HELIOGEN BLUE L6900™, D6840™, D7080™, D7020™,PYLAM OIL BLUE™, PYLAM OIL YELLOW™ and PIGMENT BLUE I™ available fromPaul Uhlich & Co., Inc., CI Pigment Blue (PB), PB 15:3, PB 15:4, anAnthrazine Blue colorant identified as CI 69810, Special Blue X-2137,mixtures thereof, and the like.

Examples of magenta pigments include a diazo dye identified as C.I.26050, 2,9-dimethyl-substituted quinacridone, an anthraquinone dyeidentified as C.I. 60710, C.I. Dispersed Red 15, CINQUASIA MAGENTA™available from E.I. DuPont de Nemours & Co., C.I. Solvent Red 19,Pigment Red (PR) 122, PR 269, PR 185, mixtures thereof, and the like.

Examples of yellow colorants include diarylide yellow3,3-dichlorobenzidene acetoacetanilide, a monoazo pigment identified inthe Color Index as C.I. 12700, C.I. Solvent Yellow 16, a nitrophenylamine sulfonamide identified in the Color Index as Foron Yellow SE/GLN,LEMON CHROME YELLOW DCC 1026™ CI, NOVAPERM YELLOW FGL™ from sanofi,Paliogen Yellow 152, 1560 (BASF), Lithol Fast Yellow 0991K (BASF),Paliotol Yellow 1840 (BASF), Neopen Yellow (BASF), Novoperm Yellow FG 1(sanofi), Permanent Yellow YE 0305 (Paul Uhlich), Pigment Yellow 74,Lumogen Yellow D0790 (BASF), Sunsperse Yellow YHD 6001 (Sun Chemicals),SUCD-Yellow D1355 (BASF), Permanent Yellow FGL, Disperse Yellow,3,2,5-dimethoxy-4-sulfonanilide phenylazo-4′-chloro-2,5-dimethoxyacetoacetanilide, mixtures thereof, and the like.

Other colorants which may be used include the following: Paliogen Violet5100 and 5890 (BASF), Normandy Magenta RD-2400 (Paul Ulrich), PermanentViolet VT2645 (Paul Ulrich), Heliogen Green L8730 (BASF), Argyle GreenXP-111-S(Paul Ulrich), Brilliant Green Toner GR 0991 (Paul Ulrich),Lithol Scarlet D3700 (BASF), Toluidine Red (Aldrich), Scarlet forThermoplast NSD Red (Aldrich), Lithol Rubine Toner (Paul Ulrich), LitholScarlet 4440, NBD 3700 (BASF), Bon Red C (Dominion Color), RoyalBrilliant Red RD-8192 (Paul Ulrich), Oracet Pink RF (Ciba Geigy),Paliogen Red 3340 and 3871K (BASF), Lithol Fast Scarlet L4300 (BASF),Heliogen Blue D6840, D7080, K7090, K6910 and L7020 (BASF), Sudan Blue OS(BASF), Neopen Blue FF4012 (BASF), PV Fast Blue B2G01 (AmericanHoechst), Irgalite Blue BCA (Ciba Geigy), Paliogen Blue 6470 (BASF),Sudan II, III and IV (Matheson, Coleman, Bell), Sudan Orange (Aldrich),Sudan Orange 220 (BASF), Paliogen Orange 3040 (BASF), Ortho Orange OR2673 (Paul Ulrich), Paliogen Yellow 152 and 1560 (BASF), Lithol FastYellow 0991K (BASF), Paliotol Yellow 1840 (BASF), Novaperm Yellow FGL(Hoechst), Permanent Yellow YE 0305 (Paul Ulrich), Lumogen Yellow D0790(BASF), Suco-Gelb 1250 (BASF), Suco-Yellow D1355 (BASF), Suco FastYellow D1165, D1355 and D1351 (BASF), Hostaperm Pink E (Hoechst), FanalPink D4830 (BASF), Cinquasia Magenta (DuPont), Paliogen Black L99849BASF), Pigment Black K801 (BASF) and particularly carbon blacks such asREGAL® 330 (Cabot), Carbon Black 5250 and 5750 (Columbian Chemicals).

Additional useful colorants include pigments in water based dispersionssuch as those commercially available from Sun Chemical, for exampleSUNSPERSE BHD 6011 (Blue 15 Type), SUNSPERSE BHD 9312 (Pigment Blue 15),SUNSPERSE BHD 6000 (Pigment Blue 15:3 74160), SUNSPERSE GHD 9600 and GHD6004 (Pigment Green 7 74260), SUNSPERSE QHD 6040 (Pigment Red 122),SUNSPERSE RHD 9668 (Pigment Red 185), SUNSPERSE RHD 9365 and 9504(Pigment Red 57, SUNSPERSE YHD 6005 (Pigment Yellow 83), FLEXIVERSE YFD4249 (Pigment Yellow 17), SUNSPERSE YHD 6020 and 6045 (Pigment Yellow74), SUNSPERSE YHD 600 and 9604 (Pigment Yellow 14), FLEXIVERSE LFD 4343and LFD 9736 (Pigment Black 7). Other useful water based colorantdispersions include those commercially available from Clariant, forexample, HOSTAFINE Yellow GR, HOSTAFINE Black T and Black TS, HOSTAFINEBlue B2G, HOSTAFINE Rubine F6B and magenta dry pigment such as TonerMagenta 6BVP2213 and Toner Magenta E02 which can be dispersed in waterand/or surfactant prior to use.

Other useful colorants include, for example, magnetites, such as Mobaymagnetites M08029, M08960; Columbian magnetites, MAPICO BLACKS andsurface treated magnetites; Pfizer magnetites CB4799, CB5300, CB5600,MCX6369; Bayer magnetites, BAYFERROX 8600, 8610; Northern Pigmentsmagnetites, NP-604, NP-608; Magnox magnetites TMB-100 or TMB-104.

Toner Preparation

Various techniques may be used to form the toner particles of the toner,including emulsion-aggregation (EA) processes. In embodiments, an EAprocess comprises aggregating a mixture comprising a latex, a colorant,and optionally, a wax, and then coalescing the aggregated mixture. Anyof the latexes described above may be used, including a single type oflatex or combinations of different types of latexes, each comprising adifferent type of resin particles. The colorant and wax may be utilizedas aqueous dispersions as described above. The mixture may behomogenized during the EA process, which may be accomplished by mixingat about 600 to about 6,000 revolutions per minute.

Aggregation may be achieved by adding any suitable aggregating agent(coagulant) to the mixture. The aggregating agent may be an inorganiccationic coagulant, such as, for example, a polyaluminum halide, such aspolyaluminum chloride (PAC) or the corresponding bromide, fluoride oriodide; a polyaluminum silicate, such as, polyaluminum sulfosilicate(PASS); or a water soluble metal salt, including, aluminum chloride,aluminum nitrite, aluminum sulfate, potassium aluminum sulfate, calciumacetate, calcium chloride, calcium nitrite, calcium oxylate, calciumsulfate, magnesium acetate, magnesium nitrate, magnesium sulfate, zincacetate, zinc nitrate, zinc sulfate, zinc chloride, zinc bromide,magnesium bromide, copper chloride, copper sulfate or mixtures thereof.The aggregating agent may be added to the mixture at a temperature thatis below the T_(g) of the resin particles of the latex. The aggregatingagent may be added to the mixture in any suitable amount, e.g., in arange of from 0.05% to 5% weight of the toner particles. The aggregatingagent may be added in a solution of nitric acid or a similar acid. Tocontrol aggregation of the particles, the aggregating agent may bemetered into the mixture over time, e.g., over a period of from about 5min to about 240 min. The addition of the aggregating agent may beaccomplished with continued homogenization. The mixture may be furtherhomogenized after addition.

The particles may be permitted to aggregate until a predetermineddesired particle size is obtained. A predetermined desired size refersto the desired particle size to be obtained as determined prior toformation, and the particle size may be monitored during the growthprocess. Samples may be taken during the growth process and analyzed,for example, with a Nanotracm 252, for D₅₀ particle size. Theaggregation may proceed by maintaining the mixture at an elevatedtemperature, or slowly raising the temperature to, e.g., from about 40°C. to about 100° C., and holding the mixture at this temperature for aperiod of time, e.g., from about 0.5 hours to about 10 hours, whilemaintaining stirring or homogenization, to provide the aggregatedparticles. Once the predetermined desired particle size is reached, thegrowth process is halted. The D₅₀ particles size of the particles maybe, for example, from about 3 μm to about 10 μm, from about 3 μm toabout 8 μm, or from about 3 μm to about 6 μm.

Shell Resin

In embodiments, after aggregation, but prior to coalescence, a resincoating may be applied to the aggregated particles (core) to form ashell thereover. The shell is applied by using any of the latexesdescribed above. The shell latex may be different from the core latex,but this isn't required. The resin particles of the shell latex and theresin particles of the core latex may differ from one another, e.g., byhaving different onset glass transition temperature T_(g) values,different M_(w)/M_(n) molecular weights, being crosslinked or beinguncrosslinked, and combinations thereof.

Once the desired final size of the toner particles is achieved, the pHof the mixture may be adjusted with a pH control agent to a value of,e.g., from about 3 to about 10. Suitable pH control agents includevarious bases including alkali metal hydroxides such as, for example,sodium hydroxide, potassium hydroxide, ammonium hydroxide, combinationsthereof, and the like. A chelating agent (sequestering agent) may alsobe added. Various suitable chelating agents may be used, such asethylenediaminetetraacetic acid (EDTA), salts of EDTA, tartaric acid,gluconal, hydroxyl-2,2′iminodisuccinic acid (HIDS), dicarboxylmethylglutamic acid (GLDA), methyl glycidyl diacetic acid (MGDA),hydroxydiethyliminodiacetic acid (HIDA), sodium gluconate, potassiumcitrate, sodium citrate, nitrotriacetate salt, humic acid, fulvic acid;alkali metal salts of EDTA, gluconic acid, oxalic acid, polyacrylates,sugar acrylates, citric acid, polyaspartic acid, diethylenetriaminepentaacetate, 3-hydroxy-4-pyridinone, dopamine, eucalyptus,iminodisuccinic acid, ethylenediaminedisuccinate, polysaccharide, sodiumethylenedinitrilotetraacetate, thiamine pyrophosphate, farnesylpyrophosphate, 2-aminoethylpyrophosphate, hydroxylethylidene-1,1-diphosphonic acid, aminotrimethylenephosphonic acid,diethylene triaminepentamethylene phosphonic acid, ethylenediaminetetramethylene phosphonic acid, mixtures thereof, and the like. Varioussuitable amounts of the chelating agent may be used, e.g., in an amountof from about 0.1% to about 1% by weight of the toner particles, fromabout 0.2% to about 0.7% by weight of the toner particles, or from about0.3% to about 0.5% by weight of the toner particles.

Coalescence

Following aggregation and application of the shell (if desired), theparticles may then be coalesced to the desired final shape, thecoalescence being achieved, by, heating the mixture to a temperature,e.g., of from about 80° C. to about 110° C., which may be at or abovethe T_(g) of the resin(s) utilized to form the toner particles. Theparticular selection of temperature is a function of the resins used.The mixture may be stirred, e.g., at from about 100 rpm to about 1,000rpm. Coalescence may be accomplished over a period of time, e.g., offrom about 1 minute to about 10 hours. The particles may be coalesceduntil a desired circularity is achieved. During coalescence, pH controlagents including various acids such as nitric acid may be used to adjustthe pH, for example, to a value of from about 3 to about 10.

After coalescence, the mixture may be cooled to room temperature, suchas from about 20° C. to about 25° C. The cooling may be rapid or slow asdesired. During cooling, pH control agents may be used to adjust the pH,e.g., to a value of from about 3 to about 10. After cooling, the tonerparticles optionally may be washed with water and then dried. Drying maybe accomplished by any suitable method including, for example,freeze-drying.

Toner particles comprising a single type of resin or more than one typeof resin are encompassed. Toner particles comprising more than one typeof resin may contain various relative amounts of the different types ofresins. In embodiments, two different types of resins are used, a firstresin being present at an amount of, e.g., from 25% to 99% by weight ofthe toner particles, and the second resin being present at an amount of,e.g., up to 35% by weight of the toner particles. This includes thefirst resin being present at an amount of from 30% to 80% by weight andfrom 40% to 70% by weight and the second resin being present at anamount of from 10% to 50% by weight and from 15% to 40% by weight. Inembodiments, the first resin forms the core of the toner particles whilethe second resin forms the shell of the toner particles.

The toner particles may contain various total amounts of resin, e.g., inan amount of from about 60% to about 95% by weight of the tonerparticles, from about 65% to about 90% by weight of the toner particles,or from about 75% to about 85% by weight of the toner particles.

The composition of the toner particles depends upon the resin(s) used.Thus, the composition of the toner particles follows that describedabove for the various resin particles.

Variations of the illustrative toner preparation processes describedabove may be applied, including those described in U.S. Pat. Nos.6,841,329 and 7,413,842, each of which is hereby incorporated byreference in its entirety, may also be used.

Additives

The toner may further contain a variety of additives to enhance theproperties of the toner. The toner may include charge additives inamounts of, e.g., from about 0.1% to about 10% by weight of the toner.Suitable charge additives include alkyl pyridinium halides, bisulfates,the charge control additives of U.S. Pat. Nos. 3,944,493; 4,007,293;4,079,014; 4,394,430 and 4,560,635, the entire disclosures of each ofwhich are hereby incorporated by reference in their entirety, negativecharge enhancing additives like aluminum complexes, any other chargeadditives, mixtures thereof, and the like.

The toner may contain surface additives. Surface additives that can beadded to the toner particles after washing or drying include, forexample, metal salts, metal salts of fatty acids, colloidal silicas,metal oxides, strontium titanates, mixtures thereof, and the like, whicheach may be present in an amount of from about 0.1% to about 10% byweight of the toner. Examples of such additives include, for example,those disclosed in U.S. Pat. Nos. 3,590,000, 3,720,617, 3,655,374 and3,983,045, the disclosures of each of which are hereby incorporated byreference in their entirety. Other additives include zinc stearate andAEROSIL R972® available from Degussa. The coated silicas of U.S. Pat.Nos. 6,190,815 and 6,004,714, the disclosures of each of which arehereby incorporated by reference in their entirety, can also be selectedin amounts, for example, of from about 0.05% to about 5% by weight ofthe toner, which additives can be added during the aggregation processor blended into the formed toner particles.

In the present disclosure, the phrases “toner” and “toner composition”refer to those compositions which are configured for use in xerographicprinters to form images therewith. Thus, in addition to the resins,colorants, present organic additives, and optional wax and other, thetoner may include any other component generally used in suchcompositions in order to form an object using the desired xerographicprinter.

The present toners may be described as being free of (i.e., notcomprising) a resin other than those provided by the resin of thepresent resin particles. This includes being free of a polyurethane, apoly(meth)acrylate (other than the resin particles themselves), apolyester or combinations thereof. A single type of resin may be used.Similarly, the toner composition itself is generally not curable and assuch, is free of (i.e., does not comprise) an initiator. This does notpreclude the presence of a minor amount of unused initiator from theresin particles or used initiator which may be incorporated into polymerchains of the resin particles. It is noted that any other exclusionsreferenced above with respect to the resin particles and latex may applyto embodiments of the toner compositions.

Toner Properties

In embodiments, the dry toner particles, exclusive of external surfaceadditives, have the following characteristics:

-   -   (1) Volume average particle diameter D₅₀ of from 2 μm to 20 μm,        from 5 μm to 15 μm, or from 5 μm to 10 μm.    -   (2) Number Average Geometric Size Distribution (GSDn) and/or        Volume Average Geometric Size Distribution (GSDv) of from 1.05        to 1.35, from 1.15 to 1.30, or from 1.20 to 1.15.    -   (3) Circularity of from 0.92 to 0.99, from 0.94 to 0.97, or from        0.95 to 0.96 (as measured with, for example, a Sysmex 3000).    -   (4) Onset glass transition temperature (T_(g)) of from 48° C. to        85° C., from 50° C. to 90° C., or from 52° C. to 85° C. (as        measured with, for example, differential scanning calorimetry).

With respect to volume average particle diameter D₅₀, GSDv, and GSDn,these characteristics may be measured using a measuring instrument suchas a Nanotrac™ 252, operated in accordance with the manufacturer'sinstructions.

Both the present latexes and toners may be characterized by theirvolatile organic content (VOC). In embodiments, the VOC content is lessthan 500 ppm as measured by Gas Chromotographic system equipped with aflame ionization detector. This includes less than 250 ppm, less than100 ppm, less than 50 ppm, and from 1 ppm to 50 ppm. The measurementincludes the amount of residual monomers and potential by-products ofthe polymerization and impurities originating from the startingmonomers.

The present toners may be characterized by their residual aluminum andsodium levels as measured using Inductively Coupled Plasma (ICP) asdescribed in the Examples, below. The aluminum levels may be less than300 ppm, less than 275 ppm, or less than 250 ppm. The sodium level maybe less than 250 ppm, less than 225 ppm, or less than 200 ppm.

Developers and Carriers

The toners may be formulated into a developer composition. Developercompositions can be prepared by mixing the toners with known carrierparticles, including coated carriers, such as steel, ferrites, and thelike. Such carriers include those disclosed in U.S. Pat. Nos. 4,937,166and 4,935,326, the entire disclosures of each of which are incorporatedherein by reference. The carriers may be present from about 2% to about8% by weight of the toner. The carrier particles can also include a corewith a polymer coating thereover, such as polymethylmethacrylate (PMMA),having dispersed therein a conductive component like conductive carbonblack. Carrier coatings include silicone resins such as methylsilsesquioxanes, fluoropolymers such as polyvinylidiene fluoride,mixtures of resins not in close proximity in the triboelectric seriessuch as polyvinylidiene fluoride and acrylics, thermosetting resins suchas acrylics, mixtures thereof and other known components.

The toners may be incorporated into a number of devices ranging fromenclosures or vessels, such as, a vial, a bottle, a flexible container,such as a bag or a package, and the like, to devices that serve morethan a storage function. The toners may be incorporated into devicesdedicated, for example, to delivering the same for a purpose, such as,forming an image. Hence, particularized toner delivery devices may beutilized, see, for example, U.S. Pat. No. 7,822,370. Such devicesinclude cartridges, tanks, reservoirs and the like, and may bereplaceable, disposable or reusable. Such a device may comprise astorage portion; a dispensing or delivery portion; and the like; alongwith various ports or openings to enable toner addition to and removalfrom the device; an optional portion for monitoring amount of toner inthe device; formed or shaped portions to enable sitting and seating ofthe device in, for example, an imaging device; and the like. A toner ofinterest may be included in a device dedicated to delivery thereof, forexample, for recharging or refilling toner in an imaging devicecomponent, such as, a cartridge, in need of toner, see, for example,U.S. Pat. No. 7,817,944, wherein the imaging device component may bereplaceable or reusable.

Imaging

The toners may be used for xerographic processes, including thosedisclosed in U.S. Pat. No. 4,295,990, the disclosure of which is herebyincorporated by reference in entirety. In embodiments, any known type ofimage development system may be used in an image developing device,including, for example, magnetic brush development, jumping singlecomponent development, two component development, hybrid scavengelessdevelopment (HSD) and the like. Those and similar development systemsare within the purview of those skilled in the art.

Imaging processes include, for example, preparing an image with axerographic device including a charging component, an imaging component,a photoconductive component, a developing component, a transfercomponent, and a fusing component. In embodiments, the developmentcomponent may include a developer prepared by mixing a carrier with atoner composition described herein. The xerographic device may include ahigh-speed printer, a black and white high-speed printer, a colorprinter, and the like.

Once the image is formed with toners/developers via a suitable imagedevelopment method such as any one of the aforementioned methods, theimage may then be transferred to an image receiving medium such as paperand the like. In embodiments, the toners may be used in developing animage in an image-developing device utilizing a fuser roll member. Fuserroll members are contact fusing devices that are within the purview ofthose skilled in the art, in which heat and pressure from the roll maybe used to fuse the toner to the image-receiving medium. In embodiments,the fuser member may be heated to a temperature above the fusingtemperature of the toner, for example to temperatures of from about 70°C. to about 160° C., after or during melting onto the image receivingsubstrate.

Use of the present latexes/resin particles is not limited to providingtoners. By way of illustration, the latex may be used to provide latexpaints. In addition to water and any of the disclosed resin particles, alatex paint generally comprises a colorant. Any of the disclosedcolorants may be used. Surfactants are also often included, such as anyof the surfactants disclosed herein. Other additives which may beincluded include fillers such as inorganic particles (e.g., silica),dispersants, defoamers, wetting agents, viscosity adjusting additives,waxes, coalescents, etc. These additives may be present at any amount toachieve a desired property for the latex paint. Any exclusions describedabove with respect to the latexes and toners may also apply toembodiments of the latex paint.

EXAMPLES

The following Examples are being submitted to further define variousspecies of the present disclosure. These Examples are intended to beillustrative only and are not intended to limit the scope of the presentdisclosure. Also, parts and percentages are by weight unless otherwiseindicated. As used herein, “room temperature” refers to a temperature offrom about 20° C. to about 25° C.

Comparative Latex Example 1

A latex comprising resin particles generated from the emulsionpolymerization of styrene, n-butyl acrylate and β-CEA was prepared asfollows. A surfactant solution containing 6.37 kilograms Dowfax 2A1(anionic surfactant) and 4096 kg deionized water was prepared by mixingfor 10 minutes in a stainless-steel holding tank. The holding tank wasthen purged with nitrogen for 5 minutes before transferring into thereactor. The reactor was then continuously purged with nitrogen whilebeing stirred at 100 RPM. The reactor was then heated up to 80° C. at acontrolled rate, and held there. Separately, 64.5 kg of ammoniumpersulfate initiator was dissolved in 359 kg of deionized water.Separately, a monomer emulsion was prepared in the following manner:3516.6 kg of styrene, 787.7 kg of butyl acrylate, 129.1 kg ofbeta-carboxylethyl acrylate (β-CEA), 30.1 kg of 1-dodecanethiol, 15.06kg of ADOD (1,10-decanediol diacrylate), 85.1 kg of Dowfax 2A1 (anionicsurfactant), and 2048 kg of deionized water were mixed to form anemulsion. One percent of the above emulsion was then slowly fed into thereactor containing the aqueous surfactant phase at 80° C. to form the“seeds” while being purged with nitrogen. The initiator solution wasthen slowly charged into the reactor and after 10 minutes the rest ofthe monomer emulsion was continuously fed in a using metering pump at arate of 0.5%/min. After 100 minutes, half of the monomer emulsion hadbeen added to the reactor. At this time, 36.18 kilograms of1-dodecanethiol was stirred into the monomer emulsion, and the monomeremulsion was continuously fed in at a rate of 0.5%/min. At this time thereactor stirrer was increased to 350 RPM. Once all the monomer emulsionis charged into the main reactor, the temperature was held at 80° C. foran additional 2 hours to complete the reaction. Full cooling was thenapplied and the reactor temperature was reduced to 35° C. The productwas collected into a holding tank. After drying the latex, the followingproperties were measured: M_(w)=33,700, M_(n)=10,900, and the onsetglass transition temperature (T_(g)) was 58.6° C. The T_(g) was measuredusing a TA Instrument Discovery Differential Scanning calorimeter 2500.For this measurement, 5-10 mg of toner sample was placed in an aluminumpan, covered with a lid and crimped shut. A reference pan and lid werealso crimped. The sample was placed in the instrument and equilibratedat 0° C. then ramped up to 150° C. at a controlled heating rate, thencooled to 0° C. and then heated again at the same rate to 150° C. Theheat flow data as a function of temperature was recorded. The glasstransition temperature of the sample was determined where the onset ofthe step transition is reported for the 2^(nd) heat.

To determine polymer molecular weight properties includingweight-average molecular weight (M_(w)), number-average molecular weight(M_(n)), and polydispersity (MWD or PDI), a Water Advanced PolymerChromatography (APC) instrument was used. The instrument is equippedwith a series of separation columns and tetrahydrofuran (THF) solvent isused as the mobile phase. Approximately 25 mg of sample is dissolved inTHF, filtered and then a portion is injected into the instrument. TheFID detector quantities the number and mass of the various polymerchains as they elute through the columns. The instrument is calibratedwith a series of polystyrene standards and is used for a relativedetermination of the molecular weight properties for the sampleanalyzed.

Comparative Latex Example 2

A latex comprising resin particles generated from the emulsionpolymerization of styrene, n-butyl acrylate and β-CEA was prepared asfollows. A surfactant solution containing 0.3352 kilograms Calfax(anionic surfactant) and 476.9 kg deionized water was prepared by mixingfor 10 minutes in a stainless-steel holding tank. The holding tank wasthen purged with nitrogen for 5 minutes before transferring into thereactor. The reactor was then continuously purged with nitrogen whilebeing stirred at 100 RPM. The reactor was then heated up to 80° C. at acontrolled rate, and held there. Separately, 1.9838 kg of ammoniumpersulfate initiator was dissolved in 14.96 kg of deionized water.Separately, a monomer emulsion was prepared as follows: 74.5767 kg ofstyrene, 24.7977 kg of butyl acrylate, 2.9849 kg of β-CEA, 48.11 kg of1-dodecanethiol, 1.8991 kg of Dowfax 2A1 (anionic surfactant), and46.9293 kg of deionized water were mixed to form an emulsion. Twopercent of the monomer emulsion was then slowly fed into the reactorcontaining the aqueous surfactant phase at 80° C. to form the “seeds”while being purged with nitrogen. The initiator solution was then slowlycharged into the reactor and after 10 minutes the rest of the emulsionwas continuously fed in using a metering pump at a rate of 0.5%/min.Once all the monomer emulsion was charged into the main reactor, thetemperature was held at 80° C. for an additional 2 hours to complete thereaction. Full cooling was then applied and the reactor temperature wasreduced to 35° C. The product was collected into a holding tank. Afterdrying the latex, the following properties were measured:M_(w)=55,000±3,000, percent solids content was 41%, and the T_(g) was55° C.±3° C.

Comparative Latex Example 3

A latex comprising resin particles generated from the emulsionpolymerization of styrene, n-butyl acrylate and β-CEA was prepared asfollows. A surfactant solution containing 605 grams of Dowfax 2A1(anionic surfactant) and 387 kg deionized water was prepared by mixingfor 10 minutes in a stainless-steel holding tank. The holding tank wasthen purged with nitrogen for 5 minutes before transferring into thereactor. The reactor was then continuously purged with nitrogen whilebeing stirred at 100 RPM. The reactor was then heated up to 80° C. at acontrolled rate, and held there. Separately, 6.1 kg of ammoniumpersulfate initiator was dissolved in 30.2 kg of de-ionized water.Separately, a monomer emulsion was prepared as follows: 311.4 kg ofstyrene, 95.6 kg of butyl acrylate, 12.21 kg of β-CEA, 2.88 kg of1-dodecanethiol, 1.42 kg of ADOD (1,10-decanediol diacrylate), 8.04 kgof Dowfax 2A1 (anionic surfactant), and 193 kg of deionized water weremixed to form an emulsion. 1% of the monomer emulsion was then slowlyfed into the reactor containing the aqueous surfactant phase at 80° C.to form the “seeds” while being purged with nitrogen. The initiatorsolution was then slowly charged into the main reactor and after 10minutes the rest of the emulsion was continuously fed into the reactorcontaining the aqueous surfactant phase using metering pump at a rate of0.5%/min, the temperature was held at 80° C. for an additional 2 hoursto complete the reaction. Full cooling was then applied and thetemperature was reduced to 35° C. The product was collected into aholding tank. After drying a portion of the latex, the followingproperties were measured: M_(w)=35,419, M_(n)=11,354, and the T_(g) was51.0° C.

Comparative Latex Example 4

A latex comprising of resin particles generated from the emulsionpolymerization of styrene, n-butyl acrylate and β-CEA was prepared asfollows. A surfactant solution containing 605 grams of Dowfax 2A1(anionic surfactant) and 387 kg deionized water was prepared by mixingfor 10 minutes in a stainless-steel holding tank. The holding tank wasthen purged with nitrogen for 5 minutes before transferring into thereactor. The reactor was then continuously purged with nitrogen whilebeing stirred at 100 RPM. The reactor was then heated up to 80° C. at acontrolled rate, and held there. Separately, 6.1 kg of ammoniumpersulfate initiator was dissolved in 30.2 kg of deionized water.Separately, a monomer emulsion was prepared as follows: 332.5 kg ofstyrene, 74.5 kg of butyl acrylate, 12.21 kg of β-CEA, 2.88 kg of1-dodecanethiol, 1.42 kg of dodecanediol diarylate (ADOD), 8.04 kgDowfax 2A1, and 193 kg of deionized water were mixed to form anemulsion. One percent of the emulsion was then slowly fed into mainreactor containing the aqueous surfactant phase at 80° C. to form the“seeds” while being purged with nitrogen. The initiator solution wasthen slowly charged into the reactor and after 10 minutes the rest ofthe emulsion was continuously fed in using a metering pump at a rate of0.5%/min. Once all the monomer emulsion was charged into the reactor,the temperature was held at 80° C. for an additional 2 hours to completethe reaction. Full cooling was then applied and the reactor temperaturewas reduced to 35° C. The product was discharged into a holding tank anddried to yield a latex having the following molecular properties:M_(w)=33,700, M_(n)=10,900 and T_(g)=58.6° C.

Latex Example 1: Synthesis of Styrene-butyl acrylate-glycerol formalmethacrylate Latex

In a 2 L buchi reactor, equipped with two P4 type impellers, 0.57 g ofDowfax 2A1 (at 47% solids) was added to 518 g deionized water (DIW). Thereactor was deoxygenated by passing a stream of nitrogen through itduring the reaction. The reactor was ramped to 77° C. and the RPM wasset to 350. Separately, in a 1 L glass vessel, equipped with two P4impellers, a monomer emulsion was prepared by mixing (at 400 rpm) 86.1 gglycerol formal methacrylate, 344 g Styrene, 143.5 g n-butyl acrylate,17.2 g b-CEA, 2.7 g n-dodecyl mercaptan (NDM, previously called DDT),9.81 g Dowfax 2A1 surfactant (at 47% solids) and 265 g DIW together.17.4 g of seed was taken from the monomer emulsion and pumped into the 2L reactor at 77° C. An initiator solution prepared from 8.61 g ofammonium persulfate in 24.3 g of DIW was added over 20 minutes after theseed emulsion addition. The remaining monomer emulsion was fed into thereactor over 120 min. Once half the monomer emulsion was added the RPMin the reactor was increased to 400 rpm. At the end of the monomer feed,the latex was held for an additional 2 hours then cooled. The resultantlatex containing 43% percent solids with a D₅₀ particle size of 217 nmwas obtained. The T_(g) of the dried latex (resin particles) was 56.2°C. Residual n-butyl acrylate monomer was 54.81 ppm; residual styrenemonomer was 37.1 ppm and residual glycerol formal methacrylate was 20.87ppm. The weight average molecular weight M_(w) was 52,574 and the numberaverage molecular weight M_(n) was 26,171.

Comparative Toner Example 1

286.9 grams of Comparative Latex Example 3 having a solids loading of41.4 weight % and 60.49 grams of a wax emulsion comprising a purifiedparaffin wax containing C42 (FNP-0092® available from Nippon Seiro)having a solids loading of 30.50 weight % were added to 613.5 grams ofdeionized water in a vessel and stirred using an IKA Ultra Turrax® T50homogenizer operating at 4,000 rpm. Thereafter, 64.1 grams of a cyanpigment dispersion PB15:3 available from Sun Chemical as Sun PigmentW51924 having a solids loading of 17 weight % was added to the reactor,followed by dropwise addition of 36 grams of a flocculent mixturecontaining 3.6 grams of polyaluminum chloride mixture and 32.4 grams ofa 0.02 molar nitric acid solution. As the flocculent mixture was addeddropwise, the homogenizer speed was increased to 5,200 rpm and thereactor contents were homogenized for an additional 5 minutes.Thereafter, the mixture was heated to a temperature of 52° C. at a rateof 1.0° C. per minute and held at 52° C. for a period of about 1.5 toabout 2 hours resulting in a cyan toner particle having a volume averageparticle size of 5 microns as measured with a Coulter Counter. Duringthe heating period, the stirrer was run at about 250 rpm. Ten minutesafter the set temperature of 49° C. was reached, the stirrer speed wasreduced to about 220 rpm.

Following this step, 134.6 grams of Comparative Latex Example 4 having asolids loading of 41.6 weight % was added to the reactor mixture andallowed to aggregate for an additional period of about 30 minutes at 51°C. to yield a cyan toner particle having a volume average particlediameter of about 5.7 microns as measured with a Coulter Counter. The pHof the reactor mixture was adjusted to pH 4.0 by using a 1.0 M sodiumhydroxide solution added to 4.82 grams of ethylene diamine tetra-aceticacid (EDTA) Versene™ 100 available from Dow having a solids loading of39 weight %. Thereafter the reactor mixture was heated at a rate of 1.0°C. per minute to a temperature of 95° C. Following this, the reactormixture was gently stirred at 95° C. for 3 hours to enable the particlesto coalesce and spherodize. After 1 hour of coalescence, the pH of thereactor was adjusted to pH 7.0 and the reactor mixture was gentlystirred for the remaining 2 hours. The reactor heater was then turnedoff and the reaction mixture was allowed to cool to room temperature ata rate of 1.0° C. per minute. The resulting toner composition wascomposed of about 16.7 percent toner particles, 0.25 percent anionicsurfactant, and about 82.9 percent water (all by weight based on thetotal weight of the toner composition). The toner particles werecomposed of 58 weight percent styrene/acrylate polymer resin (fromComparative Latex Example 3), about 28 weight percent styrene/acrylatepolymer resin (from Comparative Latex Example 4), about 5 weight percentPB15:3 pigment and about 9 weight percent FNP-0092™ wax and had a volumeaverage particle diameter of about 5.7 microns and a geometric sizedistribution (GSD) of about 1.19. The toner particles were washed 6times, wherein the first wash was conducted at a pH of 10 at 63° C.,followed by 3 washes with deionized water at room temperature, one washcarried out at a pH of 4.0 at 40° C., and finally the last wash withdeionized water at room temperature. The final measured aluminumconcentration in the dried toner particle was 265 ppm as measured byInductively Coupled Plasma Emission Spectroscopy (ICP).

Toner Example 1

278 grams of the Latex of Example 1 having a solids loading of 42.6weight %, 75 grams of a wax emulsion comprising a Fischer Tropsch wax(Q436B® available from Cytech) having a solids loading of 30 weight %,and 43 g of cyan pigment dispersion (PB15:3 available from Sun Chemical)having a solids loading of 25.6 weight % were added to 630 grams ofdeionized water in a vessel and homogenized using an IKA Ultra Turrax®T50 homogenizer operating at 4,000 rpm. During homogenization, 36 gramsof a flocculent mixture containing 3.6 grams of polyaluminum chloridemixture and 32.4 grams of a 0.02 molar nitric acid solution were addeddropwise. Thereafter, the mixture was heated to a temperature of 52° C.at a rate of 1.0° C. per minute and held for a period of about 1.5 toabout 2 hours resulting in a cyan toner particle having a volume averageparticle size of 5 microns as measured with a Coulter Counter. Duringthe heating period, the stirrer was 225 rpm until 35° C. was reached,the stirrer speed was reduced to about 200 rpm.

Following this step, 131.6 grams of the Latex of Example 1 was added tothe reactor mixture and allowed to aggregate for an additional period ofabout 60 minutes at 56° C. to yield a cyan toner particle having avolume average particle diameter of about 5.9 microns as measured with aCoulter Counter. The pH of the reactor mixture was adjusted to pH 4.0 byusing a 1.0 M sodium hydroxide solution followed by 4.82 grams ofethylene diamine tetra-acetic acid (EDTA) Versene™ 100 available fromDow having a solids loading of 39 weight %. Thereafter the reactormixture was heated at a rate of 1.0° C. per minute to a temperature of95° C. Following this, the reactor mixture was gently stirred at 95° C.for 3 hours to enable the particles to coalesce and spherodize. Thereactor heater was then turned off and the reaction mixture was cooledto 63° C. to room temperature at a rate of 1.0° C. per minute. Theresulting toner composition was composed of about 16.7 percent tonerparticles, 0.25 percent anionic surfactant, and about 82.8 percent water(all by weight based on the total weight of the toner composition. Thetoner particles were composed of about 84 weight percentstyrene/acrylate polymer resin (from the Latex of Example 1), about 5weight percent PB15:3 pigment, and about 11 weight percent Q436B wax andhad a volume average particle diameter of about 5.9 microns and ageometric size distribution (GSD) of about 1.23. The particles werewashed 4 times, wherein the first wash was conducted at a pH of 9 at 63°C., followed by one wash with deionized water at room temperature, onewash carried out at a pH of 4.0 at room temperature, and finally thelast wash with deionized water at room temperature. The final measuredaluminum content was 239.89 ppm and sodium content was 192.96 ppm in thedried toner particles as measured by Inductively Coupled Plasma EmissionSpectroscopy (ICP). The T_(g) for the toner particles was 82.32° C. andthe onset of decomposition was 355.8° C. as measured by ThermalGravimetric Analysis using a TA Instruments Q5000IR TGA system operatedwith argon gas.

The word “illustrative” is used herein to mean serving as an example,instance, or illustration. Any aspect or design described herein as“illustrative” is not necessarily to be construed as preferred oradvantageous over other aspects or designs. Further, for the purposes ofthis disclosure and unless otherwise specified, “a” or “an” means “oneor more.”

If not already included, all numeric values of parameters in the presentdisclosure are proceeded by the term “about” which means approximately.This encompasses those variations inherent to the measurement of therelevant parameter as understood by those of ordinary skill in the art.This also encompasses the exact value of the disclosed numeric value andvalues that round to the disclosed numeric value.

The foregoing description of illustrative embodiments of the disclosurehas been presented for purposes of illustration and of description. Itis not intended to be exhaustive or to limit the disclosure to theprecise form disclosed, and modifications and variations are possible inlight of the above teachings or may be acquired from practice of thedisclosure. The embodiments were chosen and described in order toexplain the principles of the disclosure and as practical applicationsof the disclosure to enable one skilled in the art to utilize thedisclosure in various embodiments and with various modifications assuited to the particular use contemplated. It is intended that the scopeof the disclosure be defined by the claims appended hereto and theirequivalents.

What is claimed is:
 1. A toner comprising toner particles, a colorant,and optionally, a wax, wherein the toner particles comprise a resincomprising a polymerization product of reactants comprising adioxane/dioxolane monomer and a vinyl co-monomer, wherein thedioxane/dioxolane monomer has Formula I or Formula II,

wherein R is selected from a group consisting of hydrogen and methyl; R′is selected from a group consisting of hydrogen and ethyl; and Z isselected from a group consisting of hydrogen, an oxygen of a carbonylgroup, an unsubstituted alkyl group, an unsubstituted aryl group, and anunsubstituted alkoxy group.
 2. The toner of claim 1, wherein Z isselected from hydrogen and an unsubstituted alkyl group.
 3. The toner ofclaim 1, wherein the dioxane/dioxolane monomer is present in the resinat an amount in a range of from about 1 weight % to about 50 weight %.4. The toner of claim 1, wherein the vinyl co-monomer comprises an alkyl(meth)acrylate present in the resin at an amount of at least about 15weight %.
 5. The toner of claim 4, wherein the alkyl (meth)acrylate isbutyl (meth)acrylate.
 6. The toner of claim 1, wherein the reactantscomprise two different types of the vinyl co-monomer.
 7. The toner ofclaim 6, wherein the two different types of the vinyl co-monomer arestyrene and an alkyl (meth)acrylate.
 8. The toner of claim 7, whereinthe alkyl (meth)acrylate is butyl (meth)acrylate.
 9. The toner of claim1, wherein the reactants comprise three different types of the vinylco-monomer.
 10. The toner of claim 9, wherein the three different typesof the vinyl co-monomer are styrene, an alkyl (meth)acrylate, and avinyl co-monomer comprising a carboxylic acid group.
 11. The toner ofclaim 10, the alkyl (meth)acrylate is butyl (meth)acrylate and the vinylco-monomer comprising the carboxylic acid group is beta-carboxyethylacrylate.
 12. The toner of claim 1, wherein the toner particles have avolume average particle diameter D₅₀ of from about 2 μm to 10 μm. 13.The toner of claim 1, wherein the toner is free of an initiator and isnot curable.
 14. The toner of claim 1, wherein the toner is free of aresin other than the resin of the toner particles.
 15. The toner ofclaim 1, wherein the resin consists of the polymerization product ofreactants consisting of the dioxane/dioxolane monomer, from one to threedifferent types of the vinyl co-monomer, and optionally, one or more ofan initiator, a chain transfer agent, and a crosslinking agent.
 16. Thetoner of claim 15, wherein the from one to three different types of thevinyl co-monomer are selected from styrene, an alkyl (meth)acrylate, andbeta-carboxyethyl acrylate.
 17. A toner comprising toner particles, acolorant, and optionally, a wax, wherein the toner particles comprise aresin comprising a polymerization product of reactants comprising adioxane/dioxolane monomer, a vinyl co-monomer, and an alkyl(meth)acrylate present in the resin at an amount of at least about 15weight %, wherein the dioxane/dioxolane monomer has Formula I or FormulaII,

wherein R is selected from a group consisting of hydrogen and methyl; R′is selected from a group consisting of hydrogen and ethyl; and Z isselected from a group consisting of hydrogen, an oxygen of a carbonylgroup, an unsubstituted alkyl group, an unsubstituted aryl group, and anunsubstituted alkoxy group.
 18. The toner of claim 17, wherein Z isselected from hydrogen and an unsubstituted alkyl group.
 19. The tonerof claim 18, wherein the alkyl (meth)acrylate is present in the resin atan amount of at least about 20 weight %.
 20. The toner of claim 19,wherein the vinyl co-monomer is styrene and the alkyl (meth)acrylate isbutyl (meth)acrylate.